Method of making impervious carbon articles



Nov. 29, 1960 P. B. DOLL ETAL Filed March 8, 1957 Porous Carbon Arricle Heai Sensitive J 50 cps. VISCOSII'Y lmEregnam Furfural,furfuryl aIcohoLefc.

{leaf to. 225 C 300 C In 24-45hours under 35-l00psr cool Cover with Granular Oxitjafion Reslsfanf Materials Hear ro l000C.fa+ raie o l0 -30C.per hour INVENTORS PII-IHI' IELB. DOLL impervious Carbon Article BY M BOBAL A T TORNEV United States Patent METHOD OF MAKING IMPERVIOUS CARBON ARTICLES Phillip B. Doll, Lakewood, and Michael A. Bobal, Cleveland, Ohio, assignors to Union Carbide Corporation, a corporation of New York Filed Mar. 8, 1957, Ser. No. 644,709

1 Claim. (Cl. 117-46) This invention relates to impervious carbon and graphite articles. More particularly this invention relates to an improved method of rendering carbon and graphite articles impervious.

The conventional method of making carbon articles comprises the formation of desired shapes from a mix of carbonaceous material and a volatile binder. The shapes are subsequently baked so that the articles may be handled without deforming. A substantial evolution of the voatile matter occurs during the baking stage leaving the article so produced porous and permeable and therefore not impervious.

The carbon industry recognizing the need for impervious carbon articles had expended large sums of money, and a great amount of time and effort to devise methods of producing carbon articles which are impervious, or at least less pervious to fluids than carbon articles produced by conventional methods. One of the methods in common use today is the impregnation of the pores of the carbon article with organic resins. Such impregnated carbon articles are generally satisfactory, if not utilized under conditions which would subject them to temperatures above about 250 C. More recently improved carbon articles, useful at temperatures well above 250 C., have been developed and a process for making such articles which involves the carbonization of the resin impregnant is disc osed in the copending application of L. L. Winter, Serial No. 644,711, filed concurrently herewith.

Although carbon articles produced by the process disclosed in the Winter application satisfy a long felt need in possessing combined properties of heat resistance, imperviousness, corrosion resistance, and strength, the Winter process, as distinguished from the articles produced by it, suffers from certain disadvantages in quality control which make the production of the final article more costly than is desirable. The difiiculties encountered in the utilization of the process are chipping, cracking and spalling of the article being treated unless the article is carefully selected as will be explained below. A high percentage of scrap material is produced by reason of the aforesaid difficulties and an increased degree of care and control is required to utilize the process commercially.

As just indicated in utilizing the process of the Winter application, careful selection of the base carbon material is necessary in order to obtain a high yield of satisfactory product. Thus, the Winter process is most satisfactory when applied to the treatment of relatively small carbon or graphite articles which are free from large voids, laminations or other physical flaws. Articles not possessing the aforesaid properties have a tendency to spall or crack during carbonization of the impregnant in the Winter process.

It is an object of this invention to provide a process by which all types and grades of carbon articles may be 2,952,386 Patented Nov. 29, 1960 ice rendered impervious without the danger of the articles spalling or cracking during processing.

Another object of this invention is to provide a process by which large sections of carbon and graphite may be rendered impervious.

Another object of this invention is to allow the use of relatively rapid rates of thermal degradation or carbonization of the resin impregnant without the danger of spallin'g or cracking.

Broadly stated. the process of this invention comprises a method in which all types and grades of carbon and graphite articles are impregnated with a liquid of low viscosity comprising a heat sensitive impregnant, preferably the thermosetting type and in which the impregnated article is heated under super-atmospheric pressure to both cure the impregnant and to effect some decomposition thereof. The article is then heated, under atmospheric pressure as above, to a temperature which is sufficient to further decompose and finally carbonize the impregnant.

The invention will be more readily understood by reference to the accompanying drawing wherein the single figure is a flow diagram illustrating the preferred method of the subject invention. Each step in this process is fully discussed in the paragraphs set forth below.

More specifically, in the practice of this invention a porous carbon article is placed in a suitable vessel and is there brought in contact with the selected impregnant. During this contact period the viscosity of the impregnant is maintained at about 50 centipoises. The impregnant preferably is caused to enter the interstitial passages of the carbon article by the application of super-atmospheric pressure to shorten the impregnation period.

After the article is saturated with impregnant, it is placed in an autoclave and is heated relative y slowly, under pressure, to a temperature of between about 225 C. and 300 C. This heating operation is herein referred to as pressure heating. During the pressure heating and at the lower end of the recited range the resin polymerizes and sets up, toward the higher temperatures of the recited range, which are h gher than the normal curing temperature of the selected impregnant, some decomposition of the impregnant occurs. Since the article has been maintained under pressure, as described above, damage to the article by spalling is avoided not only during the pressure-heating operation but also during the subsequent heating or carbonization stage to be described.

After the impregnated article is subjected to the pressure-heating operation just described it is removed from the autoclave to allow it to cool. To protect the article from oxidation during subsequent baking it is placed in a sagger and covered with a granular material, for instance coke. The sagger and the article contained therein are now heated to a temperature of at least about 1000" C. in order to continue the decomposition of the resinified impregnant and to achieve substantially complete carbonization, in situ, of the residue resulting from such decomposition. A generally satisfactory heating rate is a 10 C. to 30 C. rise per hour.

As has been indicated above, the heat treatment referred to herein as pressure heating is conducted at a temperature above the normal curing temperature of the selected impregnant. In this heating operation temperatures in the range of about 225 C. to 300 C. are reached relatively slowly, at least 24 hours being required and preferably 40 to 45 hours. Faster heating rates are suitable for resins of higher solids contents. The pressure applied during this heating operation must be high enough to prevent excessive exudation of the impregnant from the pores of the article but not high enough to unduly impede the desired intumescence of the impregnant. Pressures as low as 35 pounds per square inch have been used satisfactorily but ordinarily pressures in ated for 30 minutes to a pressure below 5 millimeters of mercury. A liquid comprising a mixture of hydrogenated monoand difurfural acetones and containing 8 percent neutral diethylsulfate was drawn into the evacuated the range of 80 to 100 pounds per square inch are pre- 5 chamber. When the pipe sections were completely covferred. ered with resin the vacuum valve was opened and 80 During the carbonization stage of the present process, to 100 pounds per square inch of air-pressure were applied the temperature may be raised to about 1000" C. in 48 for 1 hour. At the conclusion of this impregnation hours. However, it has been found that the heating rate period the resin was removed from the autoclave and is somewhat dependent on the size and shape of the article 10 the impregnated pipe sections were pressure heated to 250 being heated, thicker sections usually requiring a slower C., under about 80 to 100 pounds per square inch of air heating rise than smaller, thinner pieces. It has been pressure. The pressure-heating schedule was as follows: found that such rates of carbonization are possible with- Raised 250 to 750 C. in 1 hour, held at 750 for out risk of destructlon by spalllng and cracklng of the artr- 18 hours, cle in accordancewith this invention. presumably because Raised e to 1500 C. in 2 hours held at 1500 for the pressure heatlng cycle is more effective because 1t 1s 3 hours, carried beyond the normal resin-curing temperatures. Raised 1560 to 2000 C. in 1 hour, held at 2000 for Typical examples of the type of lmpregnants which 6 hours; may be utilized 1n the present process are furan-ketone Raised 2009 to in 6 hours, held at a for condensanon products, such as a m1xture of hydrogenated 20 6 hours monoand difurfural acetones; furfural; furfuryl alcohol; phenolaldehyde condensation products, such as phenol- After the pressure-heating stage of the process was formaldehyde; urea-aldehyde condensation products; Plete the impregnated P p Sections were remeved from epoxy resins such as polyglycidyl th rf polyhyd ic the autoclave and allowed to cool. To protect the pipe phenols and dextrose, an acid hydrolyzed starch. Hows ti s m oxidation, t y were placed in a sagger ever, any impregnant which has a tendency to intumesce and covered With eeke- The Seggel' containing the above its curing temperature and which may be carbonized Pregneted P p Sections was heated t0 1000 in 48 on heatin at el vated temperatures may b utilized i th hours, to carbonize the impregnant within the interstitial present process. passages of the pipe sections. The pipe sections processed Altho gh a substantial and useful reduction in permein accordance to the aforesaid treatment were tested and ability of an article is achieved in one treatment. as deretreated until y were found to be impervious when scribed, it is more usual that one of more additional Subjected t 50 Pounds P square inch of Pressurecycles may be required to achieve complete impervious- Data Observed during Processing in aeeol'danee with new Example I just described are presented in Table I below.

The process of this invention has been tested thorough. AS above indicated, the data show the percentage incre- 1y by application to a wide variety of starting materials mental weight gain of the material being tested after P utilizing, in different tests, different impregnants. Many Sure heating and the eel'henizing Operatien- A180 Set tests have been conducted utilizing commercial equipment forth in the table are the Observed porosities 0f the P p and test pieces of commercial size. Typical of procedures sections to be treated. These porosities were determined conducted on such a scale is that to be described below 40 by the mercury porosimeter method of H. L. Retter and in Example I. In the operations there described a num- Drake outlined in "Industrial and Engineering ber of pipe sections of a selected type were used in a single Ch mist y. Analytical Edition, P g Volume test and carried through the test as a lot or unit of which 1945- Table I Before Treatment Percent Incremental Alter Weight, Gain Treat- Pipe N0. of ments Grade Type Pipe 'Ireat- Are No. Ap Total ments Alter The Alter The Complete, parent Percent Pressure Carhoniza- Apparent Density Porosity Heating tlon Density Stage Stage 1. carbon---. 1.10 15.7 1 8.8 4.8 2 graphite... 1.69 22.0 g 1 8.4 4.3 a -.-do- L68 20.8 g 8:? 9 9 0.2 0. 01 1 10.6 5.5 4. -.-t1o 1.04 10.1 3 3:3 13 0.05 0.02

1 Approximation.

there were four lots of different grades. In each test, From Table I it can be seen that the amount of carbon the pipe sections, after determination of their average deposited by a single treatment decreases as the article is porosity and average initial apparent density, were Subjected to an increasing number of treatments, in an weighed as a unit, impregnated as described, pressure exceptional case where a greater pickup is encountered heated, weighed, carbonized, and weighed again. The in a successive single treatment it is due to the fact that percentage incremental weight gains observed after each 70 the exterior of the pipe was purposely abraded with sandoperation are set forth in Table I.

EXAMPLE I Carbon and graphite pipe sections of an inch I.D.x1% of an inch O.D.x1() inches long, were placed in paper before reimpregnation in order to insure maximum penetration of the resin. It is also evident from the data in the table that the process of this invention is applicable to a variety of materials, whether of relatively low or high density or relatively low or high porosity.

an autoclave. The chamber of the autoclave was evacu- By repetitive cycles of impregnation, pressure-heating and carbonization, impervious articles can be prepared from porous starting materials.

By the utilization of the present process it has been found that impervious carbon articles of any type may be made from any grade of stock, extruded or molded, hollow or solid, without spalling or cracking of the article during processing. It has also been found that the size of the article does not impede the successful application of this process; carbon articles with circular cross sections up to 42 inches in diameter are presently being successfully processed by this invention. The present process is attractive commercially because poorer grades of stock rendered impervious by the present process generally possess greater strength after treatment and the present process makes possible the production of carbon articles in a routine manner without excessive scrap loss.

What is claimed is:

A method of reducing the permeability of porous, large-sized carbon articles, comprising impregnating said articles with a heat-sensitive impregnant selected from the group consisting of furfural, furfuryl alcohol, phenolaldehyde condensation products, furan-ketone condensation products, epoxy resins and urea formaldehyde condensation products, said impregnant being maintained at a viscosity of about 50 centipoises while in contact with said articles; heating said articles to a temperature in the range of about 225 C. to about 300 C. during a heating a period ranging from about 24 to about 45 hours under a pressure ranging from about to about pounds per square inch to polymerize, cure, and at least partially degrade said impregnant; cooling the heated articles; placing the cooled articles in a sagger; covering the articles with granular oxidation-resistant materials; and then gradually heating said impregnated articles at a rate of 10 C. to 30 C. rise per hour under non-oxidizing conditions to a final temperature of about 1000 C; to carbonize the residue produced in the pores of said carbon articles by said first heating stage.

References Cited in the file of this patent UNITED STATES PATENTS 490,954 Edison Jan. 31, 1893 916,905 Whitney Mar. 30, 1909 942,852 Boekeland Dec. 7, 1909 1,014,882 Jones Ian. 16, 1912' 1,556,990 Henry Oct. 13, 1925 1,620,940 Bleecker Mar. 15, 1927 1,804,052 Haas May 5, 1931 2,066,176 Girvin et al Dec. 29, 1936 2,087,724 Sanders July 20, 1937 2,174,887 Kiefer Oct. 3, 1939 2,224,724 Elsey Dec. 10, 1940 FOREIGN PATENTS 757,883 Great Britain Sept. 26,1956

UNITED STATES PATENT OFFICE CERTIFICATION OF CGRRECTION Patent No. 2,962,386 November 29, 1960 Phillip Bo Doll et a1,

It is hereby certified that error appears in the above numbered patent requiring correction and that the said Letters Patent should read as corrected below'.

Column 5, line 28, strike out "a'h Signed and sealed this 13th day of June 1961,

(SEAL) Attest:

ERNEST W. SWIDER DAVID L. LADD Attesting Officer Commissioner of Patents 

